Method and means for treating textiles



United States Patent 3,150,000 METHOD AND MEANS FOR TREATING TEXTILESHeinz Enders, Stadtbergen, near Augsburg, Hans Ruile, N eusass, nearAugsburg, Hans Karl Wiest, Gersthofen, and Hans Deiner and Eugen Kurz,Augsburg, Germany, assignors to Chemische Fabrik Pfersee G.m.b.H.,Augsburg, Germany, a firm of Germany No Drawing. Filed Aug. 8, 1961,Set. N0.129,952 7 Claims. (Cl. 117-139.5)

This invention relates to a method of treating textiles, and is moreparticularly concerned with textile finishing methods.

Tex-tile materials can 'be made stain repellant, and particularly oiland grease repellant, by treating them with aqueous solutions ordispersions of organic compounds which contain a plurality ofperfluoroalkyl radicals, each radical'having'at least four carbon atoms.The stain and oil resistance of such treated textiles and other fibrousmaterial are impaired by laundering at elevated temperatures. Theaforementioned perfluoroalkyl compounds also impart some waterrepellency to the treated material, but'the water repellency achieveddoes not satisfy the usual commercial requirements. -It is anadditionalshortcoming of textile treating baths prepared from known solutions ordispersions of perfluoroalkyl compounds that they tend to form coatingson the rolls of padding ma- :chines and similar apparatus employed inthe impregnation of textiles with the solution. Such coatings must beremoved from time to time to avoid staining of the treated goods, andcontinuous operation is very difficult if at all possible.

It has now been found that the aforementoined disadvantages of the knownperfluoroaikyl compounds can be overcome while fully retaining theirfavorable effects on textiles by adding additional materials to theaqueous solutions or dispersions of these compounds. The aqueous textiletreating baths of the invention contain as active ingredients a firstorganic compound having a plurality of perfiuoroalkyl radicals, eachradical having at least four carbon atoms; a secondorganic compoundwhich is .an amine derivative having at least two urea radicalsconnected by alkylene radicals having two to four carbon atoms, aplurality of methylol radicals, and at least one alkyl radical of atleast ten, and preferably of eleven to twenty-two carbon atoms, themethylol radicals and the last mentioned alkyl radical being bound tothe nitrogen atoms of the urea radicals; and a third organic compoundwhich is-a water insoluble precondensate of an aminotriazine having atleast two amine radicals on the triazine ring which is free of directlyattached hydroxyl groups, with formaldehyde and a monohydric loweralkanol having one to five carbon atoms. The precondensate which issoluble in dilute monocarboxylic lower alkanoic acids contains for eachtriazine ring at least one alkyl radical having more than ten, andpreferably 11 to 22carbon atoms, and at least 0.2 mol equivalent of thebasic amino groups of an alkanolamine of the formula wherein .Ris'hydrogen, an alkyl radical having one to four carbon atoms, ahydroxyalkyl radical having two to four carbon atoms, the radical --CH-CH -NR R droxyalkyl radical having two to four carbon atoms; and R ishydrogen or ahydroxyalkyl radical having twoto four.carbon atoms.

The lower aikanoic acids'in which the aforementioned precondensates aresoluble include formic and acetic acids.

.tinuous; padding possible. -in the stain. and oil repellentpropertiesof the treated ma- .terial, and the finish produced has substantiallyincreased .or vinyl radical.

integer between one and three.

3,150,000 Patented Sept. 22, 1 964 ice resistance to laundering.

In the treatment of textile materials with an improved treating bath ofthe invention, the material is saturated with the aqueous dispersions orsolutions of the organic chemical compounds, the excess liquid isremoved, the textile material is dried atabout C., and the resin formingmaterials are cured at temperatures of about t to C.

The known perfiuoroalkylcompounds which may be employed in the method ofthe invention include the water-soluble chromium coordination complexesof saturated perfluoroinated monocarboxylic acids or substitutedcarboxylic acids which contain at least one perfiuoroalkyl radical of atleast four carbon atoms, and have been'disclosed in U.S. Patent No.2,662,835; also the waterdispersible basic aluminium salts of saturatedperfluorinated monocarboxylic acids or substituted carboxylic acidswhich contain at least one perfluoroalkyl radical with at least fourcarbon atoms; the water dispersible polymers or copolymers of esters of1,1-dihydroperfluoroalkanols with acrylic acid as disclosed in US.Patent No. 2,642,416; aqueous dispersions of polymers or copolymers, themonomer units having the formula RrS0zN-R"CHg-OZ wherein R is aperfluoroalkyl radical having at least four carbon atoms, R is hydrogenor an aliphatic hydrocarbon radical having one to six carbon atoms, R isan aliphatic hydrocarbon radical having one to twelve carbon a atoms,and Z is a radical of acrylic or methacrylic acid; and aqueousdispersions of polymers or copolymers, the monomer units having theformula R -SOgN-R"C 0 OX wherein-R R", and R represent the aboveradicals, and X is a polymerisable radical such as an allyl, methallylThe expression copolymer means that at least 50 mol percent of themonomer units have a periluoroalkyl group of at least 4 carbon atoms.

The amine derivatives suitable for the method of the invention may beprepared by reacting an amine having at least two basic nitrogen atomscarrying each at least one hydrogen atom, and connected by saturateddivalent alkylene radicals having two to four carbon atoms, to getherwith at least one mol of urea for each mol of the amine at about 130 C.until between 1.0 and 1.3 mols ammonia are liberated per mol urea,disolving the reaction product in water, and mixing the aqueous solutionat about40 C. with an alkyl isocyanate the alkyl radical -of which hasmore than ten, and preferably eleven to twenty-two carbon atoms, thequantity of isocyanate employed being at least one molfor each mol ofthe reaction product. Finally, at least two mols formaldehyde are addedin the form of a neutral aqueous solution.

The amine employed in preparing the amine derivative has the formulawherein): is aninteger between two and four, and y is an Diethylenetriamine is the preferred amine employed, but all alkylene diamines andpolyalkylene :po;lyamines :which satisfy the above formula areoperative.

triazine such as melamine is heated to 110 to 140 C. to-

gether-with one to two mols of an aliphatic monocarboxylic acid havingmore than ten, and preferably 15 to 19 carbon atoms; 6 to 18 mols, andpreferably 915 moles paraformaldehyde; 0.2 to 1.2, and preferably 0.5 to1.0 mol of an alkanolamine, preferably of the formula wherein R is ahydroxyalkyl radical having 2 or 3 carbon atoms, and R is hydrogen, or ahydroxyalkyl radical having two or three carbon atoms; and with amonohydric lower alkanol having one to five carbon atoms. The volatileingredients are permitted to distill off during heatting, and theresidue is further heated until a sample becomes clearly soluble in adilute monocarboxylic lower alkanoic acid, and more specifically in hot5 to percent aqueous acetic acid.

The aliphatic monocarboxylic acid having more than ten carbon atoms maybe replaced in the above reaction by an equavalent amount, that is, byone half to one mol of the corresponding anhydride.

The same precondensates are arrived at when the aminotriazine and thealiphatic monocarboxylic acid having more than then carbon atoms or theanhyride of the latter are replaced by an aminotriazine derivative inwhich one to three hydrogen atoms of the amino groups are replaced byaliphatic acyl radicals having more than ten, and preferably to 19carbon atoms.

According to another method, a methylolaminotriazine, and particularly amethylol melamine is etherified with a lower alkanol having one to fourcarbon atoms. One mol of the etherified methylol melamine is reactedwith one to two mols of a monocarboxylic aliphatic acid having more thanten carbon atoms, preferably 15 to 19 carbon atoms, at a temperature of130 to 200 C. Heating is preferably continued until substantially theentire fatty acid is present in the combined form. This reaction may beperformed at ambient pressure or in a vacuum. The intermediate productobtained is heated with 0.2 to 1.2 mols, preferably 0.5 to 1.0 mol of analkanolamine which preferably has the formula wherein R, and R representthe radicals indicated above, to a reaction temperature of 100 to 130C., until the condensation product formed is soluble in a dilute aqueousmonocarboxylic alkanoic acid such as acetic acid.

According to yet another method, one mol of a 2,4-diamino-6-alkyl-1,3,5-triazine 1 is heated with paraformaldehydepreferably in amounts of 5 to 8 mols, with 0.2 to 1.2 mols, andpreferably with 0.4 to 1.0 mol of an alkanolamine which is preferably ofthe formula wherein R, and R have the same meaning, and with a lowermonohydric alkanol having one to five carbon atoms. The volatileconstituents are permitted to distill from the reaction mixture, andheating is continued until the product is soluble in a dilutemonocarboxylic acid, and

V particularly in hot five to ten percent aqueous acetic acid.

The alkyl radical has more than 10, particularly 1122 carbon atoms.

A further method of synthesizing the pre-condensates of the inventionstarts with an aminotriazine derivative which is obtained by reactingone mol of a compound of the formula wherein E is hydrogen, aminoradical, alkyl radical with 1 to 22 carbon atoms; with at least 1 mol ofan alkyl isocyanate per mol of said aminotriazine derivative and at mostone mol of said alkyl isocyanate per equivalent amino radicals.Especially used are derivatives obtained by heating one mol of melaminewith 1.2 to 2 mols of said alkylisocyanate.

The alkyl radical of said alkyl isocyanate has more than ten, andpreferably fifteen to nineteen carbon atoms.

The reaction is performed at 200 to 260 C. until a clear liquid isobtained.

One mol of this intermediate aminotriazine derivative obtained is heatedto to C. with six to eighteen (preferably nine to fifteen) molsparaformaldehyde, 0.2 to 2.0 (preferably 0.7 to 1.5) mols of analkanolamine, preferably of the formula wherein R,, and R have the samemeaning, and a lower monohydric alkanol having at most five carbon atomsand preferably four carbon atoms. The volatile constituents arepermitted to evaporate from the solution, and heating is continued untilthe product is soluble in dilute monocarboxylic acids, such as hot fiveto ten percent aqueous acetic acid.

The test for completion of the precondensation reaction may be performedmost conveniently with 5 to 30 percent aqueous solutions of formic oracetic acid. The test is carried out by adding the precondensationproduct to the hot aqueous solution of the carboxylic acid, or by addingthe pre-condensate to the acid solution in the cold, and by heating themixture.

In making up a textile treating bath, we prefer to employ 6 to 10 gr.per liter of the perfiuoroalkyl compounds. A concentration of 2 to 15gr. will be satisfactory in most instances.

The amount of the amine derivative may be between 1 and 15 gr. for bestresults although these limits are not critical, and the concentration ofthe water-insoluble precondensate is preferably of the order of 1 to 10gr. per liter. Those skilled in the art will appreciate that theseconcentration figures do not constitute limits of operativeness, but aremerely provided for guidance while the nature of the material treatedwill determine optimum values of concentration for the effect which maybe desired. Amounts of the precondensate as small as 0.2 percent basedon the weight of the amine derivative present have a clearly observablebeneficial effect on the storage life of the treating baths, and reducethe tendency of the bath to coat squeeze rolls on processing machinery.

The water insoluble precondensates are preferably premixed withapproximately equal weights of substantially water insoluble liquidorganic solvents such as hydrocarbons andhalogenated hydrocarbons, orwith materials of similar chemical composition such as waxes andparaffin which themselves are finishing agents that make fabric waterrepellent.

It is generally more convenient to prepare a textile treating bath frompre-mixed concentrates of the amine derivatives with the solvent dilutedprecondensates in the manner described in our copending applicationSerial No. 127,903, filed July 31, 1961, now US. Patent No. 3,116,-

263. Such concentrates are distinguished by their stability in storage.

Finishing treatment with the baths of the invention can be combined withconventional wrinkle proofing treatments which are commonly applied tofibrous cellulosic materials made both from native cellulose and fromrayon. The treating baths then contain not only the combination oforganic compounds of the invention, but also the conventionalpolymerizable resin forming compounds and suitable polymerizaitoncatalysts. The simultaneous presence of wrinkle proofing resins on thetreated cellulosic fibers further enhances their resistance to stainingand to water. The combined treatment is also beneficial to fibrousmaterials which do not essenitally consist of cellulose.

The resin forming polymerizable compounds which are compatible with thetreating baths of the invention include the usual precondensates offormaldehyde with urea, melamine, ethylene urea, triazones, and thelike, their ethers, and mixtures thereof.

The catalysts that may safely be employed for curing the precondensatesin the presence of the combination of compounds of the invention includethe ammonium salts of strong acids, and such divalent metal salts asmagnesium chloride, zinc chloride, Zinc nitrate, as well as salts ofmultivalent metals, for example, aluminium or zirconium. The textilematerials are treated in the combined treating baths in the same manneras described hereinbefore.

Where a particularly soft hand and exceptional draping qualities aredesired, the treating method of the invention may be further modified byadding to the treating baths of the invention small amounts ofdispersions of N- alkyl-N,N-alkylene ureas having an alkyl radical ofmore than ten, preferably of 11 to 22 carbon atoms, and mostconveniently of 15 to 18 carbon atoms and whose alkylene radicals havetwo or three carbon atoms. The dispersions may be stabilized by addednon-volatile, strongly basic compounds, or volatile bases in combinationwith quaternary ammonium compounds of the formula wherein A is an alkylradical having more than 10 carbon atoms, B is pyridine or hydroxyethylmorpholine, and D is the monobasic anion of an acid. The dispersions areadded to the treating bath in an amount to make the concentration of theN-alkyl-N',N'-alkylene urea about one to five grams per liter.

The dispersions of the N-alkyl-N',N'-alkylene ureas are more convenientto handle and have better shelf life when they contain theafore-described preco-ndensates, as has been more fully disclosed inU.S. Patent No. 2,302,- 283.

The term, textiles and other fibrous materials as used herein, will beunderstood to include woven and knitted fabrics as Well as felt andother non-woven fabrics, paper and the like, yarns and threads, as wellas loose fibers and the intermediate agglomerations of fibers producedin the course of the transformation of fibers into fabrics. The termwill also be understood to cover fiber forming materials of natural orsynthetic origin.

The textiles and other fibrous materials treated according to theinvention are dstinguished by their water and oil repellency, but alsoby their stain resistance. Surface stains produced by alcoholicbeverages including red wine, by coifee, meat sauces, butter, oils, andtar can be wiped olf with a rag moistened with water or a conventionalstain removing solvent. The solvent is not absorbed by the treatedtextile material, and thus doesnot form unsightly rings.

The invention will be further illustrated by examples of specificembodiments thereof, but the invention is not limited to the examples.In these examples, reference Will be had to water repellency and oilrepellency ratings of treated materials. Water absorption is reported astested on the Bundesmann apparatus, and water repellency ratings areassigned asfollows:

Excellent water repellency means no sign of wetting after ten minutestesting on the Bundesmann apparatus:

Good water repellency means that signs of incipient wetting are shownafter ten minutes;

No Water repellency is the rating applied to fibrous material wettedafter ten minutes.

Oil repellency is reported as tested by placing drops of differentmixtures of purified mineral oil (Nujol) and n-heptane on the fabric orfibrous material. The drop containing the highest percentage n-heptanewhich does not wet the tested materials determines the rating on anarbitrary scale as follows.

Parts and percentages in the examples are by weight unless stateddilferently. All temperatures are in degrees EXAMPLE 1 103 partsofdiethyiene triamine and parts of urea are mixed in a flask. The mixtureis heated with stirring to about When the temperature exceeds 95 to 100,the mixture becomes a clear liquid. At the same temperature evolution ofammonia begins. The ammonia liberated is absorbed in an amount of 5 Nsulfuric acid equivalent to 40 parts ammonia. As soon as the acid isneutralized by the ammonia, the contents of the flask are poured on aplate and solidify on cooling. 50 parts of this reaction product aredissolved in 505 parts of water at about 40. parts of octadecylisocyanate are added over a period of fifteen minutes with continuousstirring. A dispersion is formed and is stirred fifteen minutes longerat 40, and then for an hour at 70. parts of a neutral, aqueous 37percent solution of formaldehyde are added with constant stirring, andthe temperature is held at about 70 for 15 minutes. Upon cooling, apaste-like dispersion is obtained.

EXAMPLE 2 The procedure of Example 1 is repeated, but the amount ofoctadecyl isocyanate is increased to 190 parts. A similar dispersion isfinally formed.

EXAMPLE 3 146 parts of triethylene tetramine and parts of urea arereacted by heating as in Example 1 until 60 parts of ammonia aredeveloped. The condensation product is dissolved in 2660 parts of waterat about 40 and reacted with 560 parts of heptadecyl isocyanate at thattemperature for 15 minutes with vigorous agitation, and then further forabout an hour at 70. 650 parts of 37 percent formaldehyde solution areadded whereby a milky dispersion is obtained which is stirred for 20minutes at about 70, and then cooledto room temperature.

EXAMPLE 4 60 parts ethylene diamine and 120 parts urea are reacted asdescribed above until 34 parts of ammonia are evolved. 50 parts of thereaction product are dissolved in 500 parts of water, and are furtherreacted with 135 parts of octadecyl isocyanate, and then with 110 partsof 37 percent formaldehyde solution under the time and temperatureconditions specified in the preceding examples.

7 EXAMPLE 370 parts of methanol, 69 parts of triethanolamine, 187 partsof paraformaldehyde, and 63 parts of melamine are mixed in a three neckflask equipped with a descending condenser, a stirrer, and athermometer. The temperature is slowly raised with vigorous agitation.When the temperature reaches 40, 225 parts of technical stearicanhydride (acid number 3-7) are added, and the temperature is graduallyraised to 120 over a period of 2 to 3 hours While the alcohol ispermitted to distill ofi". The latter temperature is maintained until asample of the product is clearly soluble in hot 6 percent acetic acid.

Respective parts of the melt poured from the flask are mixed with equalweights of paraffin and of trichloroethylene. Upon cooling to roomtemperature, the paraffin mixture is a yellowish brown waxlike mass,whereas the mixture with trichloroethylnee is a yellowish brown liquid.

EXAMPLE 6 182 parts of methanol, 35 parts of triethanolamine, 90 partsof paraformaldehyde, and 190 parts of a technical grade ofl,3-diamino-5-hexadecyl-2,4,6-triazine which consists of 80 percent ofthe pure compound, the remainder being a mixture of fatty acid nitrileshaving an average molecular Weight of 255, are mixed in a flask as inExample 5, and heated to 140 to 145 in about two to three hours. Thealcohol partly distils oif during heating. The maximum temperature ismaintained until a sample of the product is clearly soluble in hot 6percent acetic or formic acid.

Portions of the liquid contents of the reaction vessel are respectively,mixed while hot with equal Weights of parafiin, and of a mixture of onepart by volume of tetrachlorethylene and three parts by volume ofbenzene.

EXAMPLE 7 One mol melamin and two mols heptadecyl isocyanate are heatedto 240 in a three neck flask fitted with a stirrer, reflux condenser,and thermometer, until the reaction is completed. 150 parts of thereaction product are mixed in the flask with 525 parts isobutanol, 35parts diethanolamine, and 90 parts paraformaldehyde, and are refluxedfor three hours. The reflux condenser is replaced by a descendingcondenser and the temperature is slowly raised to 150 to 155 over aperiod of two to three hours. The excess of alcohol is permitted todistil off. When a sample of the contents of the flask becomes solublein hot 6 percent acetic acid, heating is discon tinned.

Portions of the hot precondensate are mixed respectively with equalweights of paraflin and of toluene.

EXAMPLE 8 100 parts dipalmitoyl melamine, 55 parts paraformaldehyde, 200parts propanol, and 20 parts triisopropanolamine are stirred and heatedto about 140 to 145 in the same manner as in the preceding examplesuntil the product is soluble in hot 6 percent acetic acid. The

product is mixed with 150 parts of monochlorobenzene.

EXAMPLE 9 Sample pieces of a cotton poplin are respectively saturatedWith different finishing baths, are extracted to a pick up ofapproximately 65 percent of a three roll padder, dried in an oven at120, and cured five minutes at 150.

The cotton fabric which is of the type commonly employed for rain coatsweighs 160 grams per square meter prior to the treatment, it has 58 yarnthreads per cm. (Nm. 77), and 24 filling threads per cm. (Nm. 65).

Finishing Bath A 40 grams of the paste like dispersion of Example 1 aremixed with 2 g. of 60 percent acetic acid, then with approximately fivevolumes of water at 80, and finally with five volumes of cold water, andthe mixture is added to a solution containing 200 g. water, 25 g.isopropanol and 15 g. isobutanol.

5 g. of the solution of the product of Example 6 in tetrachlorethyleneand benzene is mixed with 2.5 g. of 60 percent acetic acid, and tenvolumes of water are gradually added to the mixture With vigorousstirring. The emulsion obtained is added to the above solution. 25 g. ofan aqueous 30 percent emulsion of a perfluoroalkyl compound are lastadded to the composition in small amounts with stirring, and the volumeis finally adjusted to 1000 ml. by the addition of cold water.

The perfluoroalkyl compound is the polymerization product of the monomerof the formula Finishing Bath B The procedure used in preparing bath Ais followed but g. of a formaldehyde melamine precondensate containingabout 68 percent hexamethylolamine etherified about 80 percent withmethanol is dissolved in the solution of isopropanol and isobutanol inwater before the dispersion of Example 1 is added thereto. Before thefinal volume is adjusted to 1000 ml., ml. of a 10 percent solution ofmagnesium chloride hexahydrate are carefully added with agitation.

Finishing Bath C TABLE I B ath Initial After day After launderingcleaning Oil repellency Water absorption Water rcpeilency Recovery angle(average of warp and filling).

During application of baths A and B no desposits are formed on the rollsof the padder. During application of bath C a coating is formed on therolls which make pad ding difiicult after a very short run.

EXAMPLE 10 A nylon fabric having a linen weave and weighing 48 g. persquare meter (45 warp threads per cm, 38 filling threads per cm., bothNm. 207) is saturated with the finishing hath given below, extracted toa pick-up of 55 percent, dried at 120, and cured at for five minutes.

The bath is prepared as follows:

40 g. of the product of Example 2 are mixed by stirring with 4 g. of 60percent acetic acid, then with five volumes of water at 80. The mixtureis added to 500 g. water containing 25 g. isobutanol.

10 g. of the mixture of a precondensate with parafiin produced accordingto Example 1, and 10 g. water are jointly heated until the paraflinmixture is molten, 2 g. cold 60 percent acetic acid are added withvigorous agitation, and the dispersion formed is diluted with five timesits volume of water of 70 to 80 added in small portions.

Five additional volumes of cold water are added, and the resultingdiluted dispersion is added to the first prepared solution.

Alternately, g. of the solvent solution produced in Example 7 aredirectly stirred into 40 g. of the product of Example 2, and the mixtureto which 4 to 5 g. cold 60 percent acetic acid are added, is dilutedwith small portions of hot water and then added to the mixture of waterand isobutanol.

To each of the two dispersions so obtained, there are added 30 g. of anapproximately 30 percent aqueous emulsion of a polymeric perfiuoroalkylcompound which is a co-polymer of 80 mol percent of the monomer ofExample 9, and 20 mol percent butadiene.

When finished with either the paraffin mixture or the solvent solutionof Example 7, the nylon fabric has an initial water repellency rating ofexcellen which is not changed by three laundry runs at 40 using adetergent solution containing 2 grams per liter of a fatty alcoholsulfonate.

The initial oil repellency rating is 100+++ with both finishes, and isnot materially reduced by three launderings with soap. Neither finishingbath causes any difficulties on the padder in extended runs. No coatingsare deposited on the rolls.

EXAMPLE 11 A cotton poplin of the type usually employed for rain wear ispadded to 65 percent pick up on a three roll padder with a finishingbath, dried on a Dungler flat frame at about 120 to 130, and finallycured on a Haas curing machine at 150 in five minutes.

The finishing bath is prepared as follows:

24 kg. of a liquid formaldehyde precondensate containing about 35percent dimethylol ethylene urea and 20 percent of a hexamethylolmelamine etherified about 80 percent with methanol are mixed with 12liters isopropanol and then with 72 liters of cold water. 16 kg. of theproduct of Example 1 are mixed with 0.8 kg. of 60 percent acetic acid,and then with a fivefold volume of water at 70 to 80 which is added insmall portions with vigorous agitation, and is followed by anotherfivefold volume of cold water. The solution obtained is added to thesolution of the precondensate.

4 kg. of the paraifin mixture obtained in Example 5 and an equal amountof water are jointly heated to 80 whereby the paraffin mixture ismolten. 1.8 kg. of 60 percent cold acetic acid are added with strongagitation, then five volumes of water at 80 to 90 in small portions, andfinally five volumes of cold water. The mixture obtained is combinedwith the previously mixed solutions.

24 kg. of an aqueous percent solution of magnesium chloride hexahydrateare added to the combined liquids, and 10 kg. of the co-polymer emulsiondescribed in the receding example are admixed with good agitation. Thetotal volume of the bath is adjusted to 400 liters.

Several thousand meters of the cotton poplin are padded with this bathat normal padding machine speeds in a continuous run without anydifiiculties from deposits or coatings on the rolls.

After being dried and cured in the usual manner, the

" fabric has a water repellency rating of excellen which is notmeasurably affected by three laundry operations with soap. The originaloil repellency is 100+-|-+, and is reduced by the laundry treatment onlyto a value of 100.

EXAMPLE 12 A finishing bath having the same processing characteristicsis obtained when the bath of 400 liters of final volume is made up fromthe following materials:

8 kg. of the product of Example 3;

1.6 kg. of the solvent containing product of Example 5 emulsified bysequential admixture of 0.8 kg. cold 60 percent acetic acid and 24liters of water added in small portions;

'10 40 kg. of a dilute aqueous dispersion of an alkylalkylene urea thepreparation of which is described below;

36 kg. of a 50 percent solution of dimethylol ethylene .urea;

4 kg. magnesium chloridehexahydrate; and

10 kg. of the aqueous emulsion of a polymeric perfluoroalkyl alkylcompound of Example 9.

The procedure of Example 11 is followed in combining the above materialswith each other and with water.

The finished cotton poplin has practically the same oil and waterrepellency properties as that treated in Exam- .ple, 11, but theaddition of the alkyl-alkylene urea to the treating bath gives it a softhand and excellent drape properties.

The afore-mentioned aqueous dispersion of an alkylalkylene urea isprepared in the following manner:

28.5 parts ethylenirnine are diluted with 125 parts distilled water andare mixed at 20 with a solution of 45 parts of a polyethylene glycolether (obtained by reacting glycerol triricinoleate with 30 molequivalents of ethylene oxide) in 126.5 parts distilled water and 15parts ammonium hydroxide solution (d. 0.90). A solution is formed. Whileitis vigorously stirred and cooled, 200 parts octadecylisocyanate areslowly added drop by drop. Afterthe reaction is completed, 450 partsdistilled water and 10 parts ammonium hydroxide solution are added, andthe mixture is homogenized by means of a high speed agitator. Thesolution is .made up to 1000 parts by the addition of a solution of 66parts octadecyloxymethylene-hydroxyethyl morpholinium chloride in 134parts distilled water. The dispersion formed is diluted prior to usewith an equal volume of .Water which is added carefully in smallportions.

EXAMPLE 13 A wool gabardine having a twill weave, Weighing 300 g. persquare meter, and having 27 warp threads (Nrn. 19) and 20 fillingthreads ('Nrn. 22) per cm. is saturated with the finishing bathdescribed below, extracted to a pick-up of percent, dried at to andcured five minutes at The finished woolen fabric has a water repellencyrating of excellen a water absorption of 19 percent, andan oilrepellency of 100+. The water repellency rating is not changed bylaundering the fabric three times at 40, and only little reduced bythree dry cleanings. The oil repellency is not affected by launderingnor by dry cleaning.

The treating bath is prepared as follows:

100 parts of the product of Example 4 when freshly prepared and still ata temperature of 50 are mixed with one part ofthe product of Example 8.The mixture is cooledto room temperature. 3 g. thereof are mixed with0.15 g. 60 percent acetic acid, diluted by gradual addition of 15 g. hotwater of 80, and further with 15 g. cold water. The solution obtained isadded to 700 g. water containing'25 g. isobutanol. 25 g. of the emulsionof the perfluoroalkylene polymer of. Example'9 are last added with goodagitation.

The bath may be modified by substituting equal amounts of the solventbearing products of Examples 5, 6, or.7 for the product of Example 8.The properties of the finished textile material are not'significantlyaltered by the substitution.

1 EXAMPLE 14 .additionof 3. got 60 .percent acetic acid, dispersed infivevolumes of water at. .80", and finally added to.500. g. watercontaining .25. g. isobutanol. 5g. .of the paraffin bearing product ofExample 7 are solubilized with 2.5 g.

60 percent acetic acid, diluted with hot and cold water and combinedwith the aqueous solution first prepared in the same manner as describedin more detail in Example 10. Finally, 25 g. of the copolymer emulsionof Example are added.

The fabric is saturated with the bath, extracted to 65 percent pick-up,dried at 120, and cured five minutes at 150.

The water repellency after the treatment is excellent, the oilresistency 100+++. Both ratings deteriorate only insignificantly afterrepeated laundering and dry cleaning.

Practically the same water and oil repellency is obtained together witha firmed hand if so desired when the treating bath additionally contains80 grams of a methylol melamine ether-ified with methanol as describedin Example 9, and 12 g. magnesium chloride hexahydrate.

EXAMPLE 15 100 parts of the product according to Example 1 are mixedwith 2 parts of the solvent containing product of Example 5 andhomogenized afterwards. 5 gr. of this aqueous dispersion are mixed with0.25 gr. of a cold aqueous 60% solution of acetic acid and with goodstirring gr. of water of 70 C. are added in small portions andafterwards diluted with 25 gr. of cold water.

This diluted dispersion is stirred into a mixture of 40 gr. isobutanoland 400 gr. cold water. Thereafter are added 35 gr. of a solution of achromium coordination complex obtained in accordance with Example 1 ofthe US. Patent 2,662,835 and cold water to make 1000 ml.

With this treating bath a woolen fabric is soaked, squeezed to a pick-upof 80%, dried at about 100 C. and cured for 5 minutes at about 130 C.

The finished fabric has initially a water absorption of 23.7% with goodwater repellency properties and an oil repellency of 100. These effectsare only slightly diminished by laundering or dry cleaning.

It should be understood of course that the foregoing disclosure relatesto only preferred embodiments of the invention and that numerousmodifications or alterations may be made therein without departing fromthe spirit and the scope of the invention as set forth in the appendedclaims.

What we claim is:

1. A method of finishing a textile material and like fibrous material,which comprises, in combination, impregnating said material with anaqueous bath containing a first organic compound which is a polymericcompound having a plurality of repeating groups, at least 50 mol percentof said groups including perfluoroalkyl radicals having at least fourcarbon atoms; a second organic compound which is an amine derivativehaving at least two urea radicals connected by an alkylene group havingtwo of four carbon atoms, a plurality of methylol radicals and an alkylradical having more than ten carbon atoms, said methylol radicals andsaid alkyl radical being bound to V the nitrogen atoms of said urearadicals; and a third wherein R is selected from the group consisting ofhydrogen, an alkyl radical having one to four carbon atoms, ahydroxyalkyl radical having two to four carthird organic compound has aconcentration in said bath of 0.002 to 10 grams and is prepared byheating one mol of a 2,4-diamino-6-alkyl-1,3,5-trizine having a 6-alkylradical of 15 to 19 carbon atoms, with 5 to 8 mols paraformaldehyde, 0.3to 0.8 mol of an alkanolamine of the formula wherein R is a hydroxyalkylradical having two to three carbon atoms, and R is selected from thegroup consisting of hydrogen and hydroxyalkyl radicals having two tothree carbon atoms, and with a monohydric lower alkanol to a temperatureof about 130 to 160 C. until the product formed is soluble in hot 5percent acetic acid.

3. A method as set forth in claim 1, wherein said third organic compoundhas a concentration of 0.002 to 10 grams in said bath and is prepared byreacting 1 mol melamine with 1 to 2 mols of an alkyl isocyanate havingan alkyl radical of 15 to 18 carbon atoms at a temperature of about 200to 260 C. until the reaction mixture is a clear liquid, and heating saidreaction mixture with 9 to 15 mols paraformaldehyde, 0.7 to 2.0 mols ofan alkanoiamine of the formula Rr-IIT-Ih Rb wherein R is a hydroxyalkylradical having two to three carbon atoms, and R is selected from thegroup consisting of hydrogen and hydroxyalkyl radicals having two tothree carbon atoms, and with a monohydric lower alkanol to a temperatureof about to 140 C. until the product formed is soluble in hot 5 percentacetic acid.

4. A method as set forth in claim 1, wherein said bath further containsa fourth organic compound which is an N-alkyl-N',N'-alkylene urea, thealkyl radical of said fourth organic compound having more than tencarbon atoms, and each of the alkylene radicals of said fourth compoundhaving two to three carbon atoms.

5. A textile material treated according to claim 1.

6. A textile material treated according to claim 4.

7. A method as set forth in claim 1, wherein said first organic compoundhas a concentration of 2 to 15 grams per liter in said bath and is apolymeric compound having a plurality of repeating groups, at least 5 0mol percent of said groups being radicals of a compound of the formulaRF- O2NRCHrO-Z wherein R is a perfluoroalkyl radical having at leastfour carbon atoms, R is a member of the group consisting of hydrogen andaliphatic hydrocarbon radicals having one to six carbon atoms, R" is analiphatic hydrocarbon radical having one to twelve carbon atoms, and Zis a member of the group consisting of acryloyl and methacryloylradicals; said second organic compound has a concentration of one tofifteen grams per liter in said bath and is prepared by heating two molsurea with one mol diethylenetriamine to a temperature of approximatelyC. until 1.0 to 1.3 mols ammonia are driven off, dissolving the materialobtained in water to produce an aqueous solution, mixing said aqueoussolution with 1 to 2 mols of an alkyl isocyanate having an alkyl groupof 15 to 18 carbon atoms, and reacting the reaction product so obtainedwith 3 to 5 mols formaldehyde in an aqueous medium; said third organiccompound has a concentration of 0.002 gram to 10 grams in said bath andis prepared by heating one mol melamine with a reactant 13 14 selectedfrom the group consisting of one to two mols to a temperature of about110 to 140 C. until the product of a fatty acid and one half to one molof a fatty acid formed is soluble in hot 5 percent acetic acid.anhydride, with nine to fifteen mols of paraformaldehyde, with 0.5 to1.0 mol of an alkanolamine of the formula References Cited in the fileOf this Patent 5 UNITED STATES PATENTS 2,314,968 Bestian et a1. Mar. 30,1943 2,642,416 Ahlbrecht et a1. June 16, 1953 wherein R is ahydroxyalkyl radical having two to three 2,662,835 Reid Dec. 15, 1953carbon atoms, and R is selected from the group consist- 2,803,615Ahlbrecht et a1. Aug. 20, 1957 ing of hydrogen and hydroxyalkyl radicalshaving two to 10 2,864,781 Albrecht at 1958 three carbon atoms, and witha monohydric lower alkanol 3,006,896 Horst et a1. Oct. 31, 1961

1. A METHOD OF FINISHING A TEXTILE MATERIAL AND LIKE FIBROUS MATERIAL,WHICH COMPRISES, IN COMBINATION, IMPREGNATING SAID MATERIAL WITH ANAQUEOUS BATH CONTAINING A FIRST ORGANIC COMPOUND WHICH IS A POLYMERICCOMPOUND HAVING A PLURALITY OF REPEATING GROUPS, AT LEAST 50 MOL PERCENTOF SAID GROUPS INCLUDING PERFLUOROALKYL RADICALS HAVING AT LEAST FOURCARBON ATOMS; A SECOND ORGANIC COMPOUND WHICH IS AN AMINE DERIVATIVEHAVING AT LEAST TWO UREA RADICALS CONNECTED BY AN ALKYLENE GROUP HAVINGTWO OF FOUR CARBON ATOMS, A PLURALITY OF METHYLOL RADICALS AND AN ALKYLRADIAL HAVING MORE THAN TEN CARBON ATOMS, SAID METHYLOL RADICALS ANDSAID ALKYL RADICAL BEING BOUND TO THE NITROGEN ATOMS OF SAID UREARADICALS; AND A THIRD ORGANIC COMPOUND WIHICH IS A WATER INSOLUBLEPRECONDENSATE OF AN AMINOTRIAZINE WITH FORMALDEHYDE AND A MONOHYDRICLOWER ALKANOL, SAID AMINOTRIAZINE HAVING AT LEAST TWO AMINO RADICALSDIRECTLY BOUND TO THE TRIAZINE RING THEREOF, SAID RING BEING FREE OFDDIRECTLY BOUND HYDROXYL RADICALS, SAID PRECONDENSATE BEING SOLUBLE IN ADILUTE AQEUOUS MONOCARBOXYLIC LOWER ALKANOIC ACID AND HAVING FOR EACHTRIAZINE RING AT LEAST ONE ALKYL RADICAL OF MORE THAN TEN CARBON ATOMS,AND AT LEAST 0.2 MOL EQUIVALENT OF THE BASIC AMINE GROUP OF ANALKANOLAMINE OF THE FORMULA